JPH03163165A - Polyamide resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a polyamide resin composition, and more particularly to an aromatic polyamide resin composition having excellent moldability.

Technical background of the invention and its problems Polyamides are widely used as engineering plastics in various industrial fields such as the automobile industry and the electrical industry due to their excellent balance of physical properties.

Among these polyamides, aromatic polyamides, such as aromatic dicarboxylic acids such as terephthalic acid,
Aromatic polyamides made of aliphatic diamines such as hexamethylene diamine have a higher melting point than aliphatic polyamides and also have superior mechanical properties, so they have been proposed for use in a wide range of fields. (Refer to Japanese Unexamined Patent Publication No. 59-53536).

Furthermore, in order to further improve the heat resistance, rigidity, etc. of such aromatic polyamides, aromatic polyamide compositions have been proposed in which fibers such as glass fibers are added to aromatic polyamides.

Such aromatic polyamides or aromatic polyamide compositions have a high melting point and low fluidity, so they must be shaped at high temperatures close to the thermal decomposition temperature, and injection molding is required. When an attempt is made to process the aromatic polyamide by molding, etc., the aromatic polyamide composition generates intense frictional heat, which causes the aromatic polyamide to thermally decompose, resulting in a decrease in molecular weight and loss of its excellent properties. There was a point. For this reason, it has been difficult to obtain thin-walled molded products or complex-shaped molded products that generate particularly intense frictional heat during the shaping process by injection molding of aromatic polyamide composites or the like.

In addition, the aromatic polyamide composition has a high relationship with the mold used during molding. Because of the poor iI type properties, there were also problems such as easy breakage during demolding, especially in thin-walled molded products.

Furthermore, because the aromatic polyamide composition has low fluidity, it cannot be smoothly fed into the molding machine from the hopper of the molding machine used for 1.1 extrusion or extrusion molding. There were also questions about the 1°C point, where the measurement accuracy of the assembly tends to become unstable and the quality of various molded products obtained by injection molding etc. tends to become uneven.

By the way, Japanese Patent Application Laid-open No. 188457/1983 describes a polyamide resin composition for thin-walled molded products as "nylon-
46, consisting of glass fiber and a lubricant, with a blending amount of glass fiber of 10 to 8 parts per 1001ffi of nylon-46.
0 part by weight, and the amount of lubricant is 0.001 to 1 part by weight per 100 parts by weight of nylon-46 and glass fiber in total.'' ing.

In addition, JP-A No. 81-188458 describes ``100 parts by weight of nylon-46, bisamides, metal salts of groups I, ■, and ■ of the periodic table of higher fatty acids, polyethylene glycol, and carbon atoms of 26 to 32. A nylon-46 resin composition for molding is described, which is characterized by comprising 0.01 to 1.0 parts by weight of a lubricant selected from aliphatic carboxylic acids or derivatives thereof.

In these publications, nylon with a high melting point is
It is described that the shapeability of No. 46 is improved and a significant decrease in molecular weight due to molding is suppressed.

Furthermore, in these publications, this nylon-46
In addition to nylon-46, nylon-46, nylon 66/6T, nylon 66/6T/6 1 (T:
It is stated in the publication that the concept includes mixtures and copolymers with copolyamides such as terephthalic acid component (2: isophthalic acid component) and the like.

However, in the polyamide resin compositions described in the above-mentioned publications, the main component polyamide is nylon-46, which is an aliphatic polyamide, and some aromatic compounds are added to such aliphatic polyamide. Even if a polyamide-based polyamide is blended, the heat resistance or melting point of the resulting polyamide resin composition will not improve much compared to the original aliphatic polyamide.

Compared to such aliphatic polyamide resin compositions,
It has a high melting point and has a certain form! How can the moldability of an aromatic polyamide composition containing the aromatic polyamide as a main component, which has a high temperature change of 1 [3], a completely different temperature, and a different molecular structure? There is no mention in the above publication as to whether this is the case.

Purpose of the Invention The present invention is intended to solve the problems associated with the prior art as described above. The object of the present invention is to provide an aromatic polyamide resin composition in which a significant decrease in molecular weight is suppressed.

Summary of the Invention The aromatic polyamide resin composition according to the present invention comprises (A)
A dicarboxylic acid component unit (a) consisting of a terephthalic acid component unit, an aromatic dicarboxylic acid component unit other than the 41i-position of the terephthalic acid component and/or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms, and an aliphatic acid component unit (B) a fibrous reinforcing agent; 0 to 200 parts by weight, and (C) at least one compound selected from the group consisting of metal salts of groups I1 and II of the Periodic Table of Higher Fatty Acids and derivatives of aliphatic carboxylic acids having 26 to 32 carbon atoms. ．． 0.
01 to 5 parts by weight.

Since the aromatic polyamide resin composition according to the present invention is composed of the above-mentioned ingots, it has excellent fluidity and mold releasability, and is also excellent in heat resistance, rigidity, etc.

Therefore, even if this composition is shaped at a high temperature, a significant decrease in molecular weight is unlikely to occur.

DETAILED DESCRIPTION OF THE INVENTION The polyamide resin composition according to the present invention will be described in detail below.

The polyamide resin composition according to the present invention contains an aromatic polyamide (A) and a fibrous reinforcing agent (B), as described below.
), in addition to the higher fatty acids Shumyojin Table 1, I, II, I
At least one compound (C) selected from group II metal salts and derivatives of aliphatic carboxylic acids having 26 to 32 carbon atoms is contained.

The aromatic polyamide (A) contained in such a polyamide resin composition is composed of, for example, a dicarboxylic acid component unit (a) and a diamine component unit (b) as shown below.

That is, this dicarboxylic acid component unit (a) may consist only of a single α terephthalic acid component, or may consist of a terephthalic acid component unit and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit. , may be composed of a terephthalic acid component unit and an aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms, and may further include a terephthalic acid component unit, an aromatic dicarboxylic acid component unit other than terephthalic acid, and an aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms. It may also consist of group dicarboxylic acid units.

Specifically, aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid,
Examples include component units derived from phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, and the like. Among the aromatic dicarboxylic acid component units other than these terephthalic acid component units, component units derived from isophthalic acid or naphthalene dicarboxylic acid are preferred,
Particularly preferred is an isophthalic acid component unit.

Furthermore, the aliphatic dicarboxylic acid component unit has 4 to 2 carbon atoms.
0, preferably 6 to 12 aliphatic dicarboxylic acids. Examples of aliphatic dicarboxylic acids used to derive such aliphatic dicarboxylic acid component units include succinic acid, adivic acid, azelaic acid, sebacic acid,
Mention may be made of decanedicarboxylic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. Among these, adipic acid is particularly preferred.

In the present invention, the dicarboxylic acid component unit (a) is composed of a terephthalic acid monomer, an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit, and/or an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms at the qt position. , the terephthalic acid component unit is contained in an amount of 40 to 100 mol %, and the aromatic dicarboxylic acid component other than the terephthalic acid component position! It is preferable that the l1, position is contained in an amount of 0 to 60 mol%. Further, it is preferable that the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is contained in an amount of 0 to 60 mol%.

As dicarboxylic acid component position (a), terephthalic acid unit, aromatic dicarboxylic acid component unit other than terephthalic acid component unit, and/or aliphatic dicarboxylic acid component tit
When these positions are contained in the above-mentioned amounts, an aromatic polyamide (
The shaped body obtained from the assembled sole containing A) has heat resistance properties such as heat aging resistance and heat distortion temperature, mechanical properties such as tensile strength, bending strength, and abrasion resistance, and physical properties such as chemical resistance and water resistance. It has particularly excellent chemical properties.

However, depending on the use of the polyamide resin composition according to the present invention, a molded article made of this composition is not required to have outstandingly excellent properties in all of the above properties, and the required properties may be moderate. In some cases.

In such a case, as the dicarboxylic acid component unit (a), the terephthalic acid component unit is contained in an amount of less than 40 mol%, and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is contained in an amount of 60 mol%. It may be contained in an amount exceeding.

In more extreme cases, dicarboxylic acid precept L11,
As a), it may consist only of aromatic dicarboxylic acid fractional units other than mono-α terephthalic acid component.

In addition, in the present invention, the dicarboxylic acid component i11 position (
As a), along with the above-mentioned terephthalic acid component units and/or aromatic dicarboxylic acid component units other than the terephthalic acid component ftl In, a small amount, for example, about 10 mol% or less, of a polyhydric carboxylic acid component at position 111 may be included. Specific examples of such a polycarboxylic acid component include tribasic acids and polybasic acids such as 1-limellitic acid and pyromellitic acid.

In the present invention, the diamine component unit (b) constituting the aromatic polyamide (A) may consist only of an aliphatic diamine component unit, or an aliphatic diamine component unit and an alicyclic diamine component! It may consist of the 1'-1 position, or it may consist only of alicyclic diamine component units.

Such an aliphatic diamine component unit may be a linear alkylene diamine component unit or a chain alkylene diamine component unit having a branching technique. Among such aliphatic diamine fraction i1t positions, linear or branched chain alkylene diamine component units having 4 to 25 carbon atoms are preferred, and more preferably linear alkylene diamine units having 6 to 18 carbon atoms are preferred. A linear or branched chain alkylene diamine component unit is preferred.

Specifically, such aliphatic diamines include, for example, l. B-diaminohexane, t. 7-diaminohbutane, 1,8-diaminooctane, 1,9-diaminononane, 1,to-diaminodecane,
i. Component units derived from linear alkylene diamines such as tt-diaminoundecane and 1,12-diaminododecane; and 1,4-diamino-1,1-dimethylbutane, 1,4-
Diaminol-1-ethylbutane, 1.4-Diamino-1.
2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1,4-diamino-2,3-dimethylbutane, 1
．． 2-diamino-1-butylethane, l,6-diamino-2,5-dimethylhexane, l,6-diamino-2.
4-dimethylhexane, 1,6-diamino-3,3-dimethylhexane, 1,6-diamino-2,2-dimethylhexane, l,6-diamino-2.2,4-trimethylhexane, l,6- Diamino-2.4.4-trimethylhexane, 1.7-diamino-2.3-dimethylhebutane, 1.7-diamino-2.4-dimethylhebutane,
1.7-diamino-2.5-dimethylhebutane, 1.7
-Diamino-2,2-dimethylhebutane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-
1.4-dimethyloctane, 1.8-diamino-2.4
-dimethyloctane, 1.8-diamino-3.4-dimethyloctane, 1.8-diamino-4.5-dimethyloctane, 1.8-diamino-2.2-dimethyloctane, 1.8-diamino-3.3- Dimethyloctane, 1.
8-diamino-4.4-dimethyloctane, L. Examples include component units derived from branched chain alkylene diamines such as S-diamino-2,4-ethylhexane and 1,9-diamino-5-methylnonane.

Among such linear or branched chain alkylene diamine component units, linear alkylene diamine component units are preferred, particularly 1,8-diaminohexane, 1,8-diaminooctane, 1. A component unit derived from one kind of linear alkylene diamines such as 10-diaminodecane and 1,12-diaminododecane or a compound of 2M1 or more is preferable.

The alicyclic diamine component unit usually has 6 to 2 carbon atoms.
5 and is a component unit derived from a diamine containing at least one alicyclic hydrocarbon ring.

Specific examples of such alicyclic diamine component at position 111 include l,3-diaminocyclohexane, 1,4-diaminocyclohexane, l,3-bis(aminomethyl)cyclohexane, and 1.4-diaminocyclohexane.
-bis(aminomethyl)cyclohexane, isophoronediamine, biperazine, 2,5-dimethylbiperazine, bis(4-aminocyclohexyl)methane, bis(4-
aminocyclohexyl)propane, 4,4゜-diamino-3,3゜-dimethyldicyclohexylpropane, 4.4゜-diamino-3,3゜-dimethyldicyclohexylmethane, 4.4゜-diamino-3,3゜-dimethyl-5, 5゜-
Dimethyldicyclohexylmethane, 4,4゜-diamino-3,3゛-dimethyl-5.5゜-
Dimethyldicyclohexylpropane, α-α-bis(4-aminocyclohexyl)-p-diisopropylbenzene, α-α-bis(4-aminocyclohexyl)mono-diisopropylbenzene, α-α-bis (4-aminocyclohexyl)-1.4-cyclohexane, α-α-bis(4-aminocyclohexyl)-1.3-
Examples include component units derived from alicyclic diamines such as cyclohexane.

Among these alicyclic diamine component units, bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, and 4,4°-diamino-3,3'-dimethyldicyclohexylmethane are preferred, and particularly bis(
4-aminocyclohexyl)methane, 1,3-bis(aminocyclohexyl)methane, t. Component units derived from alicyclic diamines such as a-bis(aminomethyl)cyclohexane are preferred.

When the dicarboxylic acid component unit (a) has a terephthalic acid component unit as a main component unit, the diamine component unit (
b) is preferably an aliphatic diamine component unit as described above.

In this way, the dicarboxylic acid component unit (a) has the terephthalic acid component unit as the main component unit, and the diamine component unit (b)
When is an aliphatic diamine component unit as described above, the following relationship exists between the carbon number of the aliphatic diamine component unit and the molar ratio of the tit position of the dicarboxylic acid component position. It is preferable that the conditions are satisfied.

That is, the aliphatic diamine component unit has 5 to 11 carbon atoms.
In the case of a linear alkylene diamine component, the terephthalic acid component unit is preferably contained in an amount of 50 to 100 mol%, and in this case, the content of other dicarboxylic acid component units is 0 to 50 mol%. be.

In this case, the other dicarboxylic acid component units may be aromatic dicarboxylic acid component units other than the terephthalic acid component units or aliphatic dicarboxylic acid component units,
Furthermore, it may be both.

More specifically, as in the case where the fit position of the aliphatic diamine component is a linear alkylene diamine component unit having 5 to 7 carbon atoms, the alkylene diamine component! When the alkylene ridge at the l position is short, the terephthalic acid fraction unit is 50 to 85.
It is preferably contained in an amount of mol%, in which case,
The content of other dicarboxylic acid components at position 11 is 15 to 50 mol%. In this case, the other dicarboxylic acid component unit may be an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit, an aliphatic dicarboxylic acid component unit, or both.

Therefore, in this case, the content of aromatic dicarboxylic acid component units other than terephthalic acid is in the range of 15 to 50 mol %, and the content of aliphatic dicarboxylic acid component units is 15 to 5 mol %.
Within the range of 0-mol%.

Furthermore, when the dicarboxylic acid component units are both, 15 to
It is within the range of 50 mol%.

When the alkylene complex has an intermediate length, such as when the aliphatic diamine component unit is an alkylene diamine fractional unit having 6 to 11 carbon atoms, preferably 6 to 10 carbon atoms, the fli-position of the dicarboxylic acid component , the terephthalic acid component unit is in an amount of 50 to 100 mol %, the aromatic dicarboxylic acid component other than terephthalic acid component i11 is in an amount of 0 to 50 mol %, and the aliphatic dicarboxylic acid component iH is in an amount of 0 to 50 mol %. Preferably, it is contained in an amount of mol%.

When the alkylene chain is relatively long, such as when the aliphatic diamine component unit is an alkylene diamine component unit having 10 to 18 carbon atoms, the dicarboxylic acid component unit is
The terephthalic acid component at position 111 is in an amount of 75 to 100 mol%, the aromatic dicarboxylic acid component units other than the terephthalic acid component units are in an amount of 0 to 25 mol%, and the aliphatic dicarboxylic acid component at position 111 is in an amount of 0 to 25 mol%. Preferably, it is contained in an amount of mol%.

As mentioned above, depending on the number of carbon atoms in the aliphatic diamine component unit, the terephthalic acid component unit contained in the 1j position of the dicarboxylic acid component, the 41st position of the aromatic dicarboxylic acid component other than the terephthalic acid component unit, and the aliphatic diamine component unit in the 41st position By selecting the molar ratio with the group dicarboxylic acid component unit, the resulting polyamide resin composition has excellent moldability, and the composition has excellent heat resistance properties such as heat aging resistance and heat distortion temperature, as well as bending strength and abrasion resistance. A molded article with excellent mechanical properties can be obtained.

The aromatic polyamide (A) used in the polyamide resin composition of the present invention usually has a limiting viscosity [η] of 0.5 d. Q/g or more,
Preferably 0.6 djl)/g or more, more preferably 0.7 to 3. Use one within the OdN/g range.

Such aromatic polyamide (A) can be produced, for example, using a conventionally known method.

For example, Polymer Rev [ews. 10,C
on-densatlon Polymers by I
r+ter 『ac1al and Solution
Methods (by P.W. Morgan) Int
er-science Publishers (196
5)) Or Makromol. Chem. ．．
47.93-113 (1961), a diacid halide of an aromatic dicarboxylic acid and a diamine from which the constituent units of the aromatic polyamide (A) described above can be derived are prepared by a solution method. Aromatic polyamide (A) can be obtained by polycondensation. Aromatic polyamide (A) can also be obtained by interfacial polymerization.

Further, an aromatic dicarboxylic acid corresponding to the aromatic dicarboxylic acid component and a diamine or a polyamide salt thereof corresponding to the diamine component unit are mixed in the presence or absence of a solvent such as water. The aromatic polyamide (A) can be obtained by polycondensation using a post-melting method under 'lE.

Furthermore, the aromatic polyamide (A) can also be obtained by producing an oligomer by using the above-mentioned melting method, etc., and then further polycondensing it by an in-phase polymerization method.

Note that the tlt position of the diamine component forming the aromatic polyamide used in the present invention may contain an aromatic diamine component unit in addition to the above-mentioned alkylene diamine component. Specific examples of the system diamine fractional unit include the ill-position of components derived from aromatic diamines such as m-xylylene diamine and p-xylylene diamine. These aromatic diamines can be used alone or in combination of 2g or more.

The polyamide resin composition of the present invention contains a fibrous reinforcing agent, if necessary. A polyamide resin composition containing a fibrous reinforcing agent in this manner has particularly excellent heat resistance and rigidity. Such fibrous reinforcing agents include organic fibers and glass fibers, carbon fibers, potassium titanate fibers,
Examples include inorganic fibers such as wollastonite, ceramic fibers, metal-coated glass fibers, metal carbide fibers, and metal fibers. Among these fibrous reinforcing agents, inorganic fibers are preferred from the viewpoint of heat resistance, and glass fibers are more preferred because of their excellent reinforcing effect.

In the present invention, the surface of the inorganic fibrous reinforcing agent as described above is coated with a silane compound such as vinyltriethoxysilane, 2-
It may be treated with aminopurtriethoxysilane, 2-glycidoxybutrimethoxysilane, or the like.

The polyamide resin composition of the present invention contains at least one compound ( C) is included.

A polyamide resin composition containing such a compound (C) has excellent molding processability, such as melt flowability, hopper penetration property, mold release property, etc., and also has excellent moldability when molding. It is extremely rare for things to be thermally decomposed.

Therefore, by using this compound (C), it is possible to easily process the polyamide resin composition into a certain shape to obtain a thin-walled molded product without causing the thermal angle q to change.

It is presumed that such compound (C) acts as a lubricant during molding of the polyamide resin composition.

Examples of metal salts of higher fatty acids of Groups ■, ■, and ■ of the periodic table mentioned above include lauric acid, myristic acid, valmitic acid, stearic acid, l2-hydroxystearic acid, and behenic acid. Salts of higher fatty acids and metals such as lithium, sodium, potassium, magnesium, barium, zinc and aluminum may be mentioned.

Among such metal salts of higher fatty acids, lithium stearate, sodium stearate, calcium stearate, magnesium stearate, lithium 12-hydroxystearate, calcium 12-hydroxystearate, and the like are preferred.

Examples of derivatives of aliphatic carboxylic acids having 26 to 32 carbon atoms include esters of carboxylic acids such as cerotic acid, montanic acid, and melissic acid with aliphatic polyhydric alcohols, partially saponified products of these esters, and Examples include metal salts of the above carboxylic acids.

Among such aliphatic carboxylic acid derivatives having 26 to 32 carbon atoms, calcium montanate, sodium montanate, lithium montanate, and partially saponified lucium montanate butylene glycol ester are preferred.

Periodic table I1 of higher fatty acids as exemplified above,
The metal salts of group (1) and the derivatives of aliphatic carboxylic acids having 26 to 32 carbon atoms may be used alone or in combination.

The polyamide resin composition of the present invention contains 0 to 200 parts by weight, preferably 0 to 150 parts by weight of the fibrous reinforcing agent (B), based on 100 parts by weight of the aromatic polyamide (A). It is also included in the Periodic Table of Higher Fatty Acids, I, I,
At least one compound (C) selected from group II and III metal salts and derivatives of carboxylic acids having 26 to 32 carbon atoms.
is 0 based on 100 parts by weight of aromatic polyamide (A)
．． It is contained in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight.

If this fibrous reinforcing agent (B) is used in an amount exceeding 200 parts by weight, the fluidity will be too low and it will be difficult to shape the product.

Furthermore, if the compound (C) is used in an amount less than 0.01 ffl parts, the resulting polyamide resin composition will not have sufficient moldability, while if it is used in an amount exceeding 5 parts by weight, the resulting polyamide resin composition will be The mechanical properties of the resin composition tend to deteriorate.

Among the aromatic polyamides (A), fibrous reinforcing agents (B), metal salts of groups I1 and II of the periodic table of higher fatty acids, and derivatives of aliphatic carboxylic acids having 26 to 32 carbon atoms, as described above. There is no particular restriction on the method of mixing at least one compound (C) selected from the following, and any known method may be employed.

The polyamide resin composition of the present invention may contain other additives depending on the desired properties, such as heat stabilizers, weather stabilizers, flame retardants, antistatic agents, etc., as long as they do not significantly reduce the properties of the composition. A nucleating agent, a coloring agent, a foaming agent, a filler, etc. can be blended.

Effects of the Invention The aromatic polyamide resin composition according to the present invention has (A)
Specific aromatic polyamide: 100 parts by weight, (B) Fibrous reinforcing agent; 0 to 200 parts by weight (C) Metal salts of groups I1 and 2 of the periodic table of higher fatty acids, carbon number 26 to 3
At least IF from among the derivatives of aliphatic carboxylic acids of 2.
ii selected compounds; 0.01-5! Since it contains a fl amount, it has excellent fluidity and mold releasability, and is also excellent in heat resistance, rigidity, etc. Therefore, even if this composition is molded at high temperatures, it is unlikely that a significant decrease in molecular weight will occur.

[Examples] The present invention will be explained below using Examples, but the present invention is not limited to these Examples.

Examples 1 to 9 and Comparative Examples 1 to 4 A heat-resistant polyamide having a composition of 70 mol% terephthalic acid and 30 mol% isophthalic acid as acid components and 100 mol% t,e-diaminohexane as a diamine component was prepared. . The intrinsic viscosity [η] of this polyamide is 1.
O clQ /g (concentrated sulfuric acid, 30°C), the melting point by DSC was 325°C.

Hereinafter, this polyamide may be referred to as PA-1.

To 100 parts by weight of this polyamide (PA-1), various compounds shown in Table 1 were mixed in the amounts shown in Table 2, and then, using a uniaxial extruder with a diameter of 30 mmφ set at a temperature of 330°C. The mixture was melt-kneaded and pelletized at an extrusion rate of 8 kg/hour.

Table 2 shows the resin pressure at the tip of the extruder during melt mixing and the intrinsic viscosity [η] of the obtained pellets.

Next, the obtained pellets were placed at a temperature of 340°C.
It was molded using a molding machine (Model 2Is-50EP manufactured by Toshiba Machine Corporation), and the mold releasability and fluidity during melting were evaluated as ¥P.

The results are shown in Table 2.

[Measurement method] Mold releasability: 100mmX 50++ImX
0. Using an 8mm flat plate mold (set temperature 120℃),
A molded product with no deformation and good release from the mold was rated 0, a partially deformed product was Δ, and a molded product with severe deformation as a whole was rated ×.

Fluidity during melting: Spiral flow mold (set temperature 70
℃), and the spiral flow value was expressed as the flow distance.

It can be said that a material with a large value has good melt flowability during molding.

Water absorption rate: According to ASTM D570, a sample was immersed in water at 23°C, and the weight increase after 24 hours was measured.

Tensile strength: Measured according to ASTM D63g.

Tensile strength after water absorption: After immersing the sample in water at 23° C. for 24 hours to absorb water, the tensile strength of the sample was determined in the same manner as above.

Heat distortion temperature: According to ASTM D648, load stress 1
It was measured under the condition of 8.6 kg/cd.

Comparative Examples 5 to 6 In Example 1, a polyamide having a composition of 100 mol % of adipic acid as the acid component and 100 mol % of 1,4-diaminobutane as the amine component was used. The intrinsic viscosity [η] of this polyamide is 1.3
d,! )/gSDSCl. : The melting point was 292°C. Hereinafter, this polyamide may be referred to as PA-2.

Set the temperature of the injection machine to 300℃, and set the injection mold temperature to 32℃.
A polyamide composite sole was prepared in the same manner as in Example 1 except that the temperature was set at 0° C., and a test was conducted in the same manner as in Example 1 using this composition.

The results are shown in Table 2.

Large Examples 10 to 17 and Comparative Examples 7 to 9 For 60 ffiffi parts of polyamide (PA-1),
40 parts by weight of glass fiber (product name: 03MA486A, manufactured by Asahi Fiberglass ■, hereinafter abbreviated as GF) and various compounds were mixed in the parts by weight shown in Table 3, and a twin shaft with a diameter of 30ff1+1φ was set at a temperature of 330°C. Using a vented extruder, the mixture was melt-kneaded using 20 kg of Nakade Jlil/Haruma to form pellets. Table 3 shows the power consumption of the melt mixing n Samurai suppressor.

Next, the obtained pellets were injected or shaped under the same conditions as in Example 1, and the obtained molded bodies were evaluated for properties such as mold releasability and fluidity during melting.

The results are shown in Table 3.

Comparative Examples 10-1l Using 70 parts by weight of polyamide (PA-2), 30 parts by weight of glass fiber (GF), and the compounds shown in Table 1, the unrolling machine was set at 300°C, and the injection molding temperature was set at 320°C.
A composition was prepared in the same manner as in Example 1 except that the following settings were made.

Next, the obtained composition was injection molded under the same conditions as in Example 1, and properties such as mold releasability and fluidity during melting were evaluated.

The results are shown in Table 3.

Examples 18-26 and Comparative Examples 12-] -5 60 mol% of terephthalic acid as acid component and 40 mol% of adipic acid 100% of l,6-diaminohexane as diamine component
A heat-resistant polyamide having a composition of mol % was prepared. The intrinsic viscosity [η] of this polyamide was 1.1 dρ/g (concentrated sulfuric acid, 30°C), and the melting point determined by DSC was 325°C.

Hereinafter, this polyamide may be referred to as PA-3.

100 parts by weight of this polyamide (PA-3) were mixed with the various compounds shown in Table 1 in terms of χ·l in the parts by weight shown in Table 4, using a uniaxial extruder with a diameter of 30 mmφ set at a temperature of 330°C. The mixture was melt-kneaded and pelletized at an extrusion rate of 8 kg/hour.

Table 4 shows the resin pressure at the tip of the extruder during melt-kneading and the intrinsic viscosity [η] of the obtained pellets.

Next, using the obtained pellets, mold releasability and melting ++! were carried out in the same manner as in the example above. The fluidity of No. 7 and the physical properties of various molded products were evaluated.

The results are shown in Table 4.

Examples 27-35 and Comparative Examples 16-18 Polyamide (
PA-3) 60 parts by weight, glass fiber (CF) 40
using the parts by weight and the amounts of various compounds shown in Table 5,
Using a twin-screw vented extruder with a diameter of 30IIIφ set at a temperature of 330° C., the mixture was melt-kneaded and pelletized at an extrusion rate of 20 kg/hour.

Next, the obtained pellets were injection molded under the same conditions as in Example 1, and the mold M-shape properties, fluidity during melting, and various physical properties of the molded products were evaluated.

The results are shown in Table 5.

Claims (1)

[Scope of Claims] 1) (A) A dicarboxylic acid consisting of a terephthalic acid component unit and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit and/or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms. An aromatic polyamide consisting of a component unit (a) and a diamine component unit (b) consisting of an aliphatic diamine component unit and/or an alicyclic diamine component unit, based on 100 parts by weight of the aromatic polyamide. (B) a fibrous reinforcing agent; 0 to 200 parts by weight; (C) a higher fatty acid metal salt of Group I, II, or III of the Periodic Table and a carbon number of 26 to 26;
1. A polyamide resin composition comprising 0.01 to 5 parts by weight of at least one compound selected from the group consisting of 32 aliphatic carboxylic acid derivatives. 2) The content of terephthalic acid component units in the dicarboxylic acid component units is within the range of 40 to 100 mol%, and the content of aromatic dicarboxylic acid component units other than terephthalic acid component units is 0 to 60 mol%. 2. The polyamide resin composition according to claim 1, wherein the content of aliphatic dicarboxylic acid component units having 4 to 20 carbon atoms is within the range of 0 to 60 mol%.